JP5303073B1 - Automatic transmission fluid for multiple vehicles - Google Patents

Abstract

式中、Ｒ_ｃおよびＲ_ｄは、独立して、（Ｃ_３〜Ｃ_１５）アルキル、シクロアルキルまたはシクロアルケニルである、によって表される。
【選択図】なしProvided is a lubricant composition that achieves both the friction durability and shudder prevention performance of a multiple vehicle transmission fluid and the low temperature viscosity limit.
A lubricant composition comprising a) a base oil, b) 2,5-dimercapto-1,3,4-thiadiazole (DMTD), a derivative of DMTD, or a mixture thereof, and c) a friction modifier. object. Friction modifier, applying at least 40% by weight of C ₁₀ -C ₃₆ vinylidene olefin and maleic acid containing olefin, first reaction product anhydride, or ester are reacted, and the first reaction product It is made by aminating the product with an effective amount of a basic nitrogen-containing compound to provide a friction modifier. C ₁₀ -C ₃₆ vinylidene olefin has the following formula:

Wherein R _c and R _d are independently represented by (C ₃ -C ₁₅ ) alkyl, cycloalkyl or cycloalkenyl.
[Selection figure] None

Description

  The present disclosure relates to lubricating compositions, additive packages, and methods for lubricating transmissions, and more particularly to lubricating fluids that meet or exceed the specifications of vehicle transmission fluids for various vehicle manufactures.

  The vehicle transmission system is suitably configured to deliver improved power transmission efficiency and improved fuel efficiency. The transmission mechanism can include a manual transmission, a conventional stepped automatic transmission, a continuously variable transmission, a double clutch transmission, or other types of vehicle transmissions. Such transmissions are typically used in conventional gasoline or diesel engine systems.

  As newer, more fuel efficient vehicles are developed, there is a constant need to change to more versatile lubrication and power transmission fluids. In addition, various manufacturers have different standards or specifications for the performance of transmission fluids that are suitable for use in their vehicle transmissions. In transmission fluids, friction durability and anti-shudder performance are important characteristics of the fluid. However, additives that improve one property of the fluid may be detrimental to another property of the fluid. For example, to improve the friction durability of the fluid, increasing the amount of friction modifier in the transmission fluid to an undesirable amount such that the fluid no longer meets the required low temperature viscosity limit, Viscosity (BV) may be increased detrimentally. Therefore, there is a need for a single fluid that can be adapted for use in various vehicle types and manufacturers and yet meet manufacturer specifications.

式中、Ｒ_ｃおよびＲ_ｄは、独立して、（Ｃ_３〜Ｃ_１５）アルキル、シクロアルキルまたはシクロアルケニルである；によって表される。 In view of the above, embodiments of the present disclosure provide a lubricant composition, a multi-vehicle transmission fluid containing the lubricant composition, and a method for making a transmission fluid comprising the lubricant composition. . The lubricant composition comprises a) a base oil; b) 2,5-dimercapto-1,3,4-thiadiazole (DMTD), a derivative of DMTD, or a mixture thereof; and c) a friction modifier. Friction modifier, applying at least 40% by weight of C ₁₀ -C ₃₆ vinylidene olefin maleic acid containing olefin, the first reaction product is reacted with an anhydride or ester, and the first reaction product Is aminated with an effective amount of a basic nitrogen-containing compound to provide a friction modifier. C ₁₀ -C ₃₆ vinylidene olefin has the following formula:

Wherein R _c and R _d are independently (C ₃ -C ₁₅ ) alkyl, cycloalkyl or cycloalkenyl.

式中、ＲｃおよびＲｄは、独立して、（Ｃ_３〜Ｃ_１５）アルキル、シクロアルキルまたはシクロアルケニルである；によって表される。変速機用潤滑流体は、開示されている実施形態の潤滑剤組成物または変速機流体を用いて調製されてよく、したがって、潤滑剤組成物または変速機流体を含んでいても、これと同一であってもよい。 Another embodiment of the present disclosure provides a vehicle transmission containing a lubricating fluid. The lubricating fluid comprises a) a base oil; b) 2,5-dimercapto-1,3,4-thiadiazole (DMTD), a derivative of DMTD, or a mixture thereof; and c) a friction modifier. Friction modifier, applying at least 40% by weight of C ₁₀ -C ₃₆ vinylidene olefin maleic acid containing olefin, the first reaction product is reacted with an anhydride or ester, and the first reaction product Is aminated with an effective amount of a basic nitrogen-containing compound to provide a friction modifier. C ₁₀ -C ₃₆ vinylidene olefin has the following formula:

Wherein Rc and Rd are independently (C ₃ -C ₁₅ ) alkyl, cycloalkyl or cycloalkenyl. The transmission lubricating fluid may be prepared using the lubricant composition or transmission fluid of the disclosed embodiments, and thus includes the same lubricant composition or transmission fluid. There may be.

式中、Ｒ_ｃおよびＲ_ｄは、独立して、（Ｃ_３〜Ｃ_１５）アルキル、シクロアルキルまたはシクロアルケニルである；によって表される。 Other embodiments of the present disclosure provide transmission fluids and methods for providing the specific multi-vehicle transmission fluids of the disclosed embodiments. The process comprises: lubricating an oil of lubricating viscosity: i) about 100 to about 2000 ppm by weight of 2,5-dimercapto-1,3,4-thiadiazole (DMTD) in terms of the sulfur content of the transmission fluid derived from component (i). ), A derivative of DMTD, or a mixture thereof; and ii) blending with about 50 to about 800 ppm of friction modifier in terms of nitrogen content, based on the total weight of the friction modifier transmission fluid. Friction modifier, applying at least 40% by weight of C ₁₀ -C ₃₆ vinylidene olefin maleic acid containing olefin, the first reaction product is reacted with an anhydride or ester, and the first reaction product Is aminated with an effective amount of a basic nitrogen-containing compound to provide a friction modifier. C ₁₀ -C ₃₆ vinylidene olefin has the following formula:

Wherein R _c and R _d are independently (C ₃ -C ₁₅ ) alkyl, cycloalkyl or cycloalkenyl.

  An advantage of the disclosed compositions and methods is that the fluid described herein containing DMTD and a friction modifier is at least one of reduced low temperature Brookfield viscosity, improved yellow metal protection and excellent corrosion protection. One, preferably all three, and having improved friction durability. This is specifically: low temperature Brookfield viscosity (BV) of less than 14,000 centipoise (cp) at −40 ° C., weight percent lead loss of less than 0.5 wt% in aluminum beaker oxidation test, and at 40 ° C. It can be exemplified by at least one, preferably all three, of the friction durability over 300 hours in the low speed friction device. In addition, the compositions and methods of the present disclosure provide SAE No. 5 while maintaining the above-mentioned Brookfield, LVFA, and lead loss performance. It is possible to provide very good high static friction performance in a two friction rig.

  Additional features and advantages of the disclosure may be set forth in part in the description that follows and / or may be learned by practice of the disclosure. The features and advantages of the disclosure may be further realized and attained by means of the elements and combinations recited in the appended claims.

  It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure as claimed.

The term “hydrocarbyl substituent” or “hydrocarbyl group” as used herein is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, the term refers to a group having a carbon atom directly attached to the rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups:
(1) Hydrocarbon substituents, ie aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic, and alicyclic substituted aromatics Substituents, as well as cyclic substituents in which the ring is completed through another part of the molecule (eg, two substituents together form an alicyclic group);
(2) Substituted hydrocarbon substituents, ie non-hydrocarbon groups that do not primarily modify hydrocarbon substituents in the context of the present invention (eg halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkyl Substituents containing mercapto, nitro, nitroso, and sulfoxy;
(3) Hetero substituents, i.e., substituents that contain other than carbon in the ring or chain composed of carbon atoms in the context of the present invention while having predominantly hydrocarbon character. Heteroatoms include sulfur, oxygen, nitrogen and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. Generally, there are at most 2, for example, at most 1 non-hydrocarbon substituent for every 10 carbon atoms in a hydrocarbyl group; typically there are no non-hydrocarbon substituents in a hydrocarbyl group.

  The term “% by weight” as used herein means the percentage that the component represents, based on the total weight of the composition containing the listed components, unless explicitly stated otherwise.

  The term “oil-soluble” or “dispersible” as used herein does not necessarily mean that the compound or additive is soluble, soluble, or miscible in oil or can be suspended in all proportions. It is not shown. However, these terms mean that the compound or additive is, for example, soluble or stably dispersible to an extent sufficient to exert the intended effect in the environment in which the oil is used. In addition, additional incorporation of other additives may allow for the incorporation of higher levels of specific additives if desired.

Throughout this disclosure, the terms “comprises”, “includes” and the like include: the following members, components, ingredients, or a list of members, components, ingredients, etc., the term “consists of” Or a closed list, such as generally defined by “consists essentially of”, as well as the following members, components, ingredients, or members, components, lists of ingredients, etc. If it is an open list that can include further members, components, components, etc. in addition to the explicitly mentioned members, components, components, etc .; clearly consider and include both individual cases I want you to understand.
Base oil

  Base oils suitable for use in forming a lubricant composition, lubricating fluid, or transmission fluid according to the present disclosure are selected from any suitable synthetic or natural oils or mixtures thereof having a suitable lubricating viscosity. Also good. Natural oils include animal and vegetable oils (eg, castor oil, lard oil) and mineral lubricating oils such as liquefied petroleum and solvent or acid treated paraffin, naphthene or mixed paraffin / naphthenic mineral lubricants. be able to. Coal or shale derived oils may also be suitable. The base oil may typically have a viscosity of about 2 to about 15 cSt, or as a further example, about 2 to about 10 cSt at 100 ° C. Furthermore, oils derived from gas liquefaction processes are also suitable.

  Suitable synthetic base oils include dicarboxylic acids, alkyl esters of polyglycols and alcohols, polyalphaolefins including polybutene, alkylbenzenes, organic esters of phosphoric acid, and polysilicone oils. Synthetic oils include hydrocarbon oils such as polymerized and copolymerized olefins (eg, polybutylene, polypropylene, propylene isobutylene copolymers, etc.); poly (1-hexene), poly (1-octene), poly (1-decene), etc. As well as mixtures thereof; alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene, etc.); polyphenyls (eg, biphenyl, terphenyl, alkylated polyphenyl, etc.); alkylated diphenyl ethers And alkylated diphenyl sulfide, and derivatives, analogs and homologues thereof.

Alkylene oxide polymers and copolymers whose terminal hydroxyl groups have been modified by esterification, etherification, etc., and their derivatives constitute another class of known synthetic oils that can be used. Such oils include oils prepared via polymerization of ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (eg, methyl-polyisopropylene glycol ether having an average molecular weight of about 1000, about 500-1000 A diphenyl ether of polyethylene glycol having a molecular weight of about 1000 to 1500, a diethyl ether of polypropylene glycol, or the like, and mono- and polycarboxylic acid esters of these polyoxyalkylene polymers, for example, acetates of tetraethylene glycol, mixed _C 3 -C ₈ fatty acid esters, or as exemplified by _{C 13} oxo acid diester.

  Another class of synthetic oils that may be used include dicarboxylic acids (eg, phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid Esters of dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) with various alcohols (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) Can be mentioned. Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, sebacic acid Examples include dieicosyl, 2-ethylhexyl diester of linoleic acid dimer, complex ester formed by reacting 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid.

Esters useful as synthetic oils are those made from C _{5 to} C ₁₂ monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol. Etc.

Thus, the base oil used that can be used to make the engine lubricant compositions described herein can be a single base oil or a mixture of two or more base oils. . In particular, the one or more base oils may desirably be selected from any of the base oils in Groups IV defined in the American Petroleum Institute (API) Base Oil Compatibility Guidelines. Such base oil groups are as follows:

  The base oil may contain a small amount or a large amount of polyalphaolefin (PAO). Typically, polyalphaolefins are derived from monomers having about 4 to about 30, about 4 to about 20, or about 6 to about 16 carbon atoms. Examples of useful PAOs include those derived from octene, decene, and mixtures thereof. The PAO may have a viscosity of about 2 to about 15, about 3 to about 12, or about 4 to about 8 cSt at 100 ° C. Examples of PAOs include 4 cSt polyalphaolefin at 100 ° C., 6 cSt polyalphaolefin at 100 ° C., and mixtures thereof. A mixture of mineral oil and the above polyalphaolefin may be used.

The base oil may be an oil derived from a Fischer-Trop synthesized hydrocarbon. Fischer Trop synthesized hydrocarbons are made from synthesis gas containing H ₂ and CO using a Fischer Trops catalyst. Such hydrocarbons typically require further processing to be useful as base oils. For example, hydrocarbons may be hydroisomerized using the process disclosed in US Pat. Nos. 6,103,099 or 6,180,575; US Pat. No. 4,943,672. Or hydroisomerization using the process disclosed in US Pat. No. 6,096,940; using the process disclosed in US Pat. No. 5,882,505. May be dewaxed; hydroisomerization and dehydration using processes disclosed in US Pat. Nos. 6,013,171; 6,080,301; or 6,165,949. May be waxed.

  Any of the natural or synthetic unrefined, refined, and rerefined oils (and mixtures of any two or more thereof) of the type disclosed above may be used in the base oil. Unrefined oils are those obtained directly from natural or synthetic sources without further purification. For example, shale oil obtained directly from a carbonization operation, petroleum oil obtained directly from primary distillation, or ester oil obtained directly from an esterification process and used without further processing is an unrefined oil. Refined oils are similar to unrefined oils except that they have been further processed in one or more refining steps to improve one or more properties. Many such purification techniques are known to those skilled in the art, such as solvent extraction, secondary distillation, acid or base extraction, filtration, permeation, and the like. The rerefined oil is obtained by a process similar to that used to obtain a refined oil that is applied to refined oil already used in operation. Such rerefined oils are also known as reclaimed or reprocessed oils and are often further processed by techniques directed to removal of spent additives, contaminants, and oil breakdown products.

The base oil may be combined with the additive composition disclosed in the embodiments herein to provide a multi-vehicle transmission fluid. Accordingly, the base oil may be in the range of greater than about 30% to about 95%, such as from about 40% to about 90%, typically greater than about 50% by weight, based on the total weight of the fluid composition. It may be present in an amount in the fluid composition described herein.
Ultra-high pressure / anti-wear additive

  In embodiments of the present disclosure, a sulfur-containing ultra-high pressure / antiwear additive component may be added to the base oil to impart a specific sulfur content to the lubricant formulation. Sulfur containing ultra high pressure / antiwear additives include, but are not limited to, thiazole, triazole and thiadiazole. Examples of such compounds include benzotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbylthio- 1,3,4-thiadiazole, 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazole, 2,5-bis (hydrocarbylthio) -1,3,4-thiadiazole, and 2,5-bis ( Hydrocarbyldithio) -1,3,4-thiadiazole. Essential features of the disclosed embodiments include: 2,5-dimercapto-1,3,4-thiadiazole (DMTD), DMTD in the lubricant composition, and / or lubricating fluid, and / or transmission fluid. Or a mixture thereof. Derivatives of DMTD include, but are not limited to, 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole or 2,5-bis- (hydrocarbyldithio) -1,3,4-thiadiazole, and mixtures thereof; Carboxylic acid ester of DMTD; condensation product of α-halogenated aliphatic monocarboxylic acid and DMTD; reaction product of unsaturated cyclic hydrocarbon and unsaturated ketone with DMTD; reaction of aldehyde and diarylamine with DMTD Product: amine salt of DMTD; derivative of dithiocarbamate of DMTD; reaction product of aldehyde with alcohol or aromatic hydroxy compound and DMTD; reaction product of aldehyde, mercaptan and DMTD; 2-hydrocarbylthio -5-mercapto-1,3,4-thiadi Tetrazole; product derived by combining the oil-soluble dispersant and DMTD; and mixtures thereof. Such compositions are described in US Pat. No. 4,612,129 and the patent literature listed herein.

  In some embodiments, the thiadiazole used in the transmission fluids described herein is 2,5-bis- (hydrocarbyldithio) -1,3,4-thiadiazole and about 85% bis-hydrocarbyl. And its mono-substituted equivalent 2-hydrocarbylthio-5-mercapto-1,3,4-thiadiazole, which is commercially available as a mixture of two compounds in a ratio of 15% monohydrocarbyl.

式中、ＲおよびＲ^１は、同じまたは異なる炭化水素であってよく、ｘおよびｙは、０〜約８の整数であり、ｘおよびｙの合計は、少なくとも１である；によって表されてよい。かかる誘導体を調製するためのプロセスは、米国特許第２，１９１，１２５号；米国特許第３，０８７，９３２号；および米国特許第２，７４９，３１１号に記載されている。上記文献において参照および記載されている反応は、いくらかの量のモノヒドロカルビルジチ
オ−チアジアゾールならびにビス−ヒドロカルビル化合物を生成することができる。これら２つの比は、反応体の量を変えることによって調整されてよい。 U.S. Pat. Nos. 2,719,125; 2,719,126; and 3,087,937 describe various 2,5-bis (hydrocarbyldithios) that are particularly desirable for the disclosed embodiments. The preparation of) -1,3,4-thiadiazole is described. Here, each hydrocarbyl group may be linked to thiadiazole via a plurality of sulfur atoms. The hydrocarbon group may be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl and alkaryl. The polysulfide has the following general formula:

Wherein R and R ¹ may be the same or different hydrocarbons, x and y are integers from 0 to about 8, and the sum of x and y is at least 1; . Processes for preparing such derivatives are described in US Pat. No. 2,191,125; US Pat. No. 3,087,932; and US Pat. No. 2,749,311. The reactions referenced and described in the above documents can produce some amount of monohydrocarbyl dithio-thiadiazole as well as bis-hydrocarbyl compounds. These two ratios may be adjusted by changing the amount of reactants.

式中、Ｒ^１は、ヒドロカルビル置換基である；を有する２−ヒドロカルビルジチオ−５−メルカプト−１，３，４−チアジアゾールの調製は、米国特許第３，６６３，５６１号に記載されている。上記組成物は、等モル部のヒドロカルビルメルカプタンおよびＤＭＴＤまたはそのアルカリ金属メルカプチドの酸化カップリングによって作製されてよい。かかる化合物の調製に用いられ得るモノメルカプタンは、式Ｒ^１ＳＨ：式中、Ｒ^１は、１〜約２８個の炭素原子を含有するヒドロカルビル基である；によって表される。酸化カップリングを促進するのに、ペルオキシ化合物、ハイポハライド、もしくは空気、またはこれらの混合物が用いられてよい。モノメルカプタンの具体例として、メチルメルカプタン、イソプロピルメルカプタン、ヘキシルメルカプタン、デシルメルカプタン、および長鎖アルキルメルカプタン、例えば、１分子あたり３〜約７０個のプロペンまたはイソブチレンを有するプロペンポリマーおよびイソブチレンポリマー、特にポリイソブチレンから誘導されるメルカプタンが挙げられる。 Particularly desirable according to the disclosed embodiments, the formula:

The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole having R ¹ is a hydrocarbyl substituent is described in US Pat. No. 3,663,561. The composition may be made by oxidative coupling of equimolar parts of hydrocarbyl mercaptan and DMTD or its alkali metal mercaptides. Monomercaptans that can be used in the preparation of such compounds are represented by the formula R ¹ SH: where R ¹ is a hydrocarbyl group containing from 1 to about 28 carbon atoms. Peroxy compounds, hypohalides, or air, or mixtures thereof may be used to promote oxidative coupling. Specific examples of monomercaptans include methyl mercaptan, isopropyl mercaptan, hexyl mercaptan, decyl mercaptan, and long chain alkyl mercaptans, such as propene and isobutylene polymers, particularly polyisobutylene, having from 3 to about 70 propene or isobutylene per molecule. Mercaptans derived from

For the transmission fluid, the amount of sulfur imparted by the sulfur-containing ultra-high pressure / antiwear additive component may range from about 100 to about 2000 ppm by weight, based on the total weight of the transmission fluid. 2,5-dimercapto-1,3,4-thiadiazole (DMTD), a derivative of DMTD, or a mixture thereof, each of about 100-based on the total weight of the lubricant composition, lubricating fluid or transmission fluid In particular, it is desirable to provide sulfur to the lubricant composition, lubricating fluid or transmission fluid in an amount in the range of about 2000 ppm by weight, for example about 350 to 1000 ppm by weight, more specifically about 400 to 800 ppm by weight. desirable.
Friction modifier

  The second component combined with the ultra high pressure / antiwear additive component includes a specific friction modifier. Friction modifiers can be used in the lubricating fluids described herein to reduce or increase friction between surfaces (eg, torque converter clutch or shift clutch members) at low slide speeds. Typically, the desired result is that the friction vs. velocity (μ-v) curve has a positive slope, which in turn results in “stick-slip” behavior (eg, shudder, noise, and harsh shift). ) To minimize clutch engagement.

  As friction modifier, aliphatic amine or ethoxylated aliphatic amine, ether amine, alkoxylated ether amine, aliphatic fatty acid amide, acylated amine, aliphatic carboxylic acid, aliphatic carboxylic acid ester, polyol ester, aliphatic carboxylic acid Examples include compounds such as ester-amides, imidazolines, tertiary amines, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphonates, aliphatic thiophosphates, where the aliphatic group is preferably an oil Usually contains one or more carbon atoms so as to be soluble. As a further example, an aliphatic group may contain about 8 or more carbon atoms. Also suitable are aliphatic substituted succinimides formed by reacting one or more aliphatic succinic acids or anhydrides with ammonia and primary amines.

式中、Ｒ_ｃおよびＲ_ｄは、独立して、（Ｃ_３〜Ｃ_１５）アルキル、シクロアルキルまたはシクロアルケニルである；によって表される。上記プロセスによると、Ｃ_１０〜Ｃ_３６ビニリデンオレフィンは、Ｃ_１０〜Ｃ_３６ビニリデンオレフィンを酸触媒作用条件下に置き、続いて、得られたオレフィンをマレイン酸、無水物、またはエステルによって熱的条件下に処理してエン反応を誘発させることによって、より熱力学的に安定な三置換の内部オレフィンに所望により変換される。 Specific friction modifier required by the embodiments disclosed is one example of a particularly desirable succinimide derived friction modifier, olefin and maleic acid containing C ₁₀ -C ₃₆ vinylidene olefins of at least 40 wt% , An anhydride, or an ester to give a first reaction product. The first reaction product is then aminated with an effective amount of a basic nitrogen-containing compound to provide a friction modifier. Friction modifier compounds made by the above process are described in more detail in US Patent Application Publication No. 2010/0137173, the disclosure of which is hereby incorporated by reference. In the above reaction, the C ₁₀ -C ₃₆ vinylidene olefin has the following formula:

Wherein R _c and R _d are independently (C ₃ -C ₁₅ ) alkyl, cycloalkyl or cycloalkenyl. According to the above _process, C 10 _{-C 36} vinylidene _olefins, place the C 10 _{-C 36} vinylidene olefin to the acid catalysis conditions, followed by resulting olefin maleic acid, thermal conditions by anhydride or ester, Subsequent treatment to induce the ene reaction optionally converts to a more thermodynamically stable trisubstituted internal olefin.

Friction modifier compounds made using the above C ₁₀ -C ₃₆ vinylidene olefins can therefore be prepared using the synthetic route summarized in Scheme I.

In the above reaction scheme, C ₁₀ -C ₃₆ vinylidene olefin (6) by placing the vinylidene acid catalysis conditions, are converted to a more thermodynamically stable trisubstituted internal olefin (5). The resulting olefin was treated under thermal conditions with maleic anhydride (4) optionally substituted at the R ₂ and R ₄ positions to provide about 0.5: 1 to about 1.5: 1. An "ene reaction" is induced at a molar ratio of vinylidene olefin to maleic acid in the range. Reaction product (3) is an alkyl succinic anhydride having a vinylmethyl group and is liberated from unreacted maleic anhydride by placing the reaction mixture under vacuum. The amination reaction may then be performed at a suitable temperature that results in acceleration of the reaction. The reaction mixture may be neutralized with an equal amount of base such as ammonia gas or substituted amine (2) at a suitable elevated temperature. The final product (1) is an alkyl succinimide having a vinylmethyl group, and is produced with an overall yield of 80% or more. Alternatively, alkyl succinic anhydride (3) reacts with polyamine species (2a) to give bis-succinimide (1a) with both succinimides substituted by alkyl groups containing vinylmethyl groups. be able to. Certain friction modifiers of the disclosed embodiments are about 50 to about 800 ppm, preferably about 150 to about 800 ppm in the transmission fluid, based on the total weight of the lubricant composition, transmission fluid, or lubricating fluid. Desirably present in the lubricant composition, transmission fluid, or lubricating fluid described herein in an amount sufficient to provide 500 ppm by weight of nitrogen.

  In one embodiment, the weight ratio of nitrogen (ppm by weight) with the succinimide friction modifier to sulfur (wt ppm) with the DMTD or DMTD derivative, or a mixture thereof is, for example, for use as a multi-vehicle transmission fluid About 0.2: 1 to about 1.2: 1, for example about 0.25: 1 to about 0.8: 1, preferably to optimize low temperature viscosity, oxidation resistance, and suitable friction durability May range from about 0.3: 1 to about 0.7: 1, or more preferably from about 0.45: 1 to about 0.67: 1.

  Other friction modifier compounds may also be included in the transmission fluids described herein. For example, one group of friction modifiers is at least one linear aliphatic hydrocarbyl group in which the N aliphatic hydrocarbyl substituent is free of acetylenic unsaturation and has in the range of about 14 to about 20 carbon atoms. Contains N-aliphatic hydrocarbyl-substituted diethanolamine.

  Other friction modifiers that may be used are (i) the same or different hydroxyalkyl groups each containing from 2 to about 4 carbon atoms and the aliphatic groups containing from about 10 to about 25 carbon atoms At least one di (hydroxyalkyl) aliphatic tertiary amine, and (ii) the hydroxyalkyl group contains from 2 to about 4 carbon atoms and the aliphatic group is about 10 Based on a combination with at least one hydroxyalkyl aliphatic imidazoline, which is a cyclic hydrocarbyl group containing from about 25 carbon atoms. For further details regarding this friction modifier system, reference should be made to US Pat. No. 5,344,579.

Generally speaking, the lubricating composition described herein is preferably up to about 2.5% by weight, desirably about 0.05% to about 2.2% by weight in the transmission fluid. In particular at most about 1.8% by weight, or at most only about 1.25% by weight, or as a further example, from about 0.75 to about 1% by weight of one or more total friction modifiers. It's okay.
Other optional ingredients

The transmission fluid described herein may also include conventional additives of the type used in automatic transmission fluid formulations in addition to the components described above. Such additives include, but are not limited to, dispersant additives, detergent additives, antioxidants, corrosion inhibitors, anti-corrosive agents, metal deactivators, antifoaming agents, pour point depressants, air entrained additives Agents, seal swelling agents and the like.
Dispersant additive

The dispersant additive that may be used may be the reaction product of a hydrocarbyl dicarboxylic acid or anhydride and a polyamine. The hydrocarbyl moiety of the hydrocarbyl dicarboxylic acid or anhydride may be derived from a butene polymer, such as a polymer of isobutylene. Suitable polyisobutenes for use herein include those formed from polyisobutylene or highly reactive isobutylene having a terminal vinylidene content of at least about 60%, such as from about 70% to more than about 90%. Suitable polyisobutenes include those prepared using a BF ₃ catalyst. The average number molecular weight of the polyalkenyl substituent is determined by gel permeation chromatography (GPC) as described above and may vary over a wide range, for example from about 100 to about 5000, such as from about 500 to about 5000.

Dicarboxylic acids or anhydrides thereof include carboxylic acid reactants other than maleic anhydride, such as maleic acid, fumaric acid, malic acid, tartaric acid, itaconic acid, itaconic acid, including corresponding acid halides and lower aliphatic esters. It may be selected from acid anhydride, citraconic acid, citraconic acid anhydride, mesaconic acid, ethylmaleic acid anhydride, dimethylmaleic acid anhydride, ethylmaleic acid, dimethylmaleic acid, hexylmaleic acid and the like. The molar ratio of maleic anhydride to hydrocarbyl moieties in the reaction mixture used to make the hydrocarbyl dicarboxylic acid or anhydride may vary widely. Thus, the molar ratio may vary from about 5: 1 to about 1: 5, such as from about 3: 1 to about 1: 3. A particularly preferred molar ratio of anhydride to hydrocarbyl moiety is from about 1: 1 to less than about 1.6: 1.

  Any one of a number of polyamines may be used in preparing the dispersant additive. Non-limiting exemplary polyamines include aminoguanidine bicarbonate (AGBC), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) and heavy polyamines. be able to. Heavy polyamines have small amounts of lower polyamine oligomers, such as TEPA and PEHA, but have more than 7 nitrogen atoms and 2 or more primary amines per molecule and are much wider than conventional polyamine mixtures. Mixtures of polyalkylene polyamines having predominantly branched oligomers may be included. Additional non-limiting polyamines that can be used to prepare hydrocarbyl substituted succinimide dispersants are disclosed in US Pat. No. 6,548,458, the disclosure of which is hereby incorporated by reference in its entirety. It is. In an embodiment of the present disclosure, the polyamine may be selected from tetraethylenepentamine (TEPA).

式中、ｎは、０または１〜５の整数を表し、Ｒ^２は、先に定義したヒドロカルビル置換基である；の化合物であってよい。一実施形態において、ｎは３であり、Ｒ^２は、ポリイソブテニル置換基、例えば、少なくとも約６０％、例えば約７０％〜約９０％超の末端ビニリデン含有量を有するポリイソブチレンから誘導されるものである。式（Ｉ）の化合物は、ヒドロカルビル置換の無水コハク酸、例えば、ポリイソブテニル無水コハク酸（ＰＩＢＳＡ）と、ポリアミン、例えばテトラエチレンペンタミン（ＴＥＰＡ）との反応生成物であってよい。 In one embodiment, the dispersant additive has the formula (I):

Wherein n represents 0 or an integer from 1 to 5 and R ² is a hydrocarbyl substituent as defined above. In one embodiment, n is 3 and R ² is derived from a polyisobutenyl substituent, eg, polyisobutylene having a terminal vinylidene content of at least about 60%, such as from about 70% to greater than about 90%. is there. The compound of formula (I) may be the reaction product of a hydrocarbyl-substituted succinic anhydride such as polyisobutenyl succinic anhydride (PIBSA) and a polyamine such as tetraethylenepentamine (TEPA).

The compound of formula (I) may have a molar ratio of (A) polyisobutenyl substituted succinic anhydride to (B) polyamine in the compound ranging from about 4: 3 to about 1:10. Particularly useful dispersants include polyisobutenyl groups of polyisobutenyl-substituted succinic anhydride having a number average molecular weight (Mn) measured by GPC in the range of about 500-5000, and (B) the general formula H ₂ N (CH ₂ ). m- [NH (CH ₂ ) _m ] _n —NH ₂ , wherein m is in the range of 2 to 4 and n is in the range of 1 to 2;

The dispersant additives described herein may be boronated and / or phosphorylated. Thus, in one embodiment, the dispersant additive has a nitrogen content of up to 10,000 ppm by weight, such as from about 0.5 to about 0.8% by weight, and from 0: 1 to about 0.8: 1. It has a weight ratio of boron + phosphorus to nitrogen ((B + P) / N). The amount of dispersant in the fluid composition may vary from about 300 to about 1000 ppm by weight in nitrogen, such as from about 400 to about 900 ppm by weight, based on the total weight of the lubricant composition.
Metal detergent

  Metal detergents that may be included in the transmission fluids described herein may generally have a polar head group with a long hydrophobic tail, which includes a metal salt of an acidic organic compound. The salt may contain a substantially stoichiometric amount of metal, in which case the salt is usually described as a normal or neutral salt and has a total base number of from about 0 to less than about 150 or TBN ( Typically as measured by ASTM D2896). A large amount of metal base may be included by reacting an excess of a metal compound such as an oxide or hydroxide with an acid gas such as carbon dioxide. The resulting overbased detergent comprises neutral detergent micelles surrounding a core of an inorganic metal base (eg, hydrated carbonate). Such overbased detergents may have a TBN of about 150 or more, such as about 150 to about 450 or more.

  Detergents that may be suitable for use in this embodiment include oil-soluble excess base lower bases, and neutral sulfonates of metals, particularly alkali or alkaline earth metals such as sodium, potassium, lithium, calcium, and magnesium. , Phenates, sulfurated phenates and salicylates. More than one metal may be present, for example both calcium and magnesium. Mixtures of calcium and / or magnesium and sodium may also be suitable. Suitable metal detergents include an excess of calcium or magnesium sulfonate with a TBN of 150-450 TBN, an excess of calcium or magnesium carbonate or magnesium with a TBN of 150-300 TBN, and a TBN of 130-350 TBN. It may be an excess of base calcium or magnesium salicylate. A mixture of such salts may also be used.

The metal-containing detergent may be present in the lubricating composition in an amount sufficient to improve the anti-rust performance of the lubricating fluid. For example, the amount of detergent in the lubricating fluid composition may range from about 0.5% to about 5% by weight. As a further example, the metal-containing detergent may be present in an amount from about 1.0% to about 3.0% by weight. The metal-containing detergent is present in the lubricating composition in an amount sufficient to impart from about 10 to about 5000 ppm alkali and / or alkaline earth metal to the lubricant composition, based on the total weight of the lubricant composition. You can do it. As a further example, the metal-containing detergent may be present in the lubricating composition in an amount sufficient to provide about 40 to about 900 ppm alkali and / or alkaline earth metal. A particularly suitable amount of detergent in the lubricating fluid composition can impart from about 60 to about 600 ppm alkali and / or alkaline earth metal to the lubricating fluid composition.
Corrosion inhibitor

  Rust or corrosion inhibitors may also be included in the transmission fluid described herein. Such materials include monocarboxylic acids and polycarboxylic acids. Examples of suitable monocarboxylic acids are octanoic acid, decanoic acid and dodecanoic acid. Suitable polycarboxylic acids include dimers and trimer acids, such as those generated from acids such as tall oil fatty acids, oleic acid, linoleic acid and the like.

Another useful class of rust inhibitors are alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as tetrapropenyl succinic acid, tetrapropenyl succinic anhydride, tetradecenyl succinic acid, tetradecenyl. Succinic anhydride, hexadecenyl succinic acid, hexadecenyl succinic anhydride and the like may be included. Also useful are half esters of alkenyl succinic acids having 8 to 24 carbon atoms in the alkenyl group with alcohols such as polyglycols. Other suitable rust or corrosion inhibitors include ether amines; acid phosphates; amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; imidazolines; aminosuccinic acid or derivatives thereof. Mixtures of such rust or corrosion inhibitors may be used. The total amount of corrosion inhibitor in the transmission fluid formulation described herein may range from about 0.01 to about 2.0 weight percent, based on the total weight of the formulation.
Antioxidant

  In some embodiments, the lubricating compositions described herein may include an antioxidant compound. Antioxidants include phenolic antioxidants, aromatic amine antioxidants, sulfurized phenolic antioxidants, and organic phosphites, among others. Examples of phenolic antioxidants include 2,6-ditert-butylphenol, a liquid mixture of tertiary butylated phenol, 2,6-ditert-butyl-4-methylphenol, 4,4′-methylenebis (2 , 6-ditert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), mixed methylene-bridged polyalkylphenol, and 4,4′-thiobis (2-methyl-6-tert-butylphenol) ). N, N'-disec-butyl-phenylenediamine, 4-isopropylaminodiphenylamine, phenyl-. alpha. -Naphthylamine, phenyl-. alpha. Naphthylamine and ring alkylated diphenylamine. Examples include sterically hindered tertiary butylated phenols, bisphenols and transdermal acid derivatives and combinations thereof.

式中、Ｒ’およびＲ’’は、それぞれ独立して、６〜３０個の炭素原子を有する置換または非置換のアリール基を表す；を有するジアリールアミンが挙げられる。アリール基の置換基の例示として、１〜３０個の炭素原子を有するアルキルなどの脂肪族炭化水素基、ヒドロキシ基、ハロゲン基、カルボン酸またはエステル基、またはニトロ基が挙げられる。 Aromatic amine antioxidants include, but are not limited to, the formula:

In the formula, R ′ and R ″ each independently represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Examples of substituents on the aryl group include aliphatic hydrocarbon groups such as alkyl having 1 to 30 carbon atoms, hydroxy groups, halogen groups, carboxylic acid or ester groups, or nitro groups.

  The aryl group is preferably substituted or unsubstituted phenyl or naphthyl, in particular one or both of the aryl groups is 4 to 30 carbon atoms, preferably 4 to 18 carbon atoms, most preferably 4 to Substituted with at least one alkyl having 9 carbon atoms. It is preferred that one or both aryl groups are substituted, eg, monoalkylated diphenylamine, dialkylated diphenylamine, or a mixture of mono and dialkylated diphenylamine.

  Examples of diarylamines that can be used include, but are not limited to: diphenylamine; various alkylated diphenylamines; 3-hydroxydiphenylamine; N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine; Dibutyl-diphenylamine; monooctyldiphenylamine; dioctyldiphenylamine; monononyldiphenylamine; dinonyldiphenylamine; monotetradecyldiphenylamine; ditetradecyldiphenylamine, phenyl-alpha-naphthylamine; monooctylphenyl-alpha-naphthylamine; phenyl-beta- Naphthylamine; monoheptyldiphenylamine; diheptyl-diphenylamine; p-oriented styrenated diphenylamine Emissions; mixed butyl octyl diphenylamine; and mixtures octyl styryl diphenylamine.

Sulfur-containing antioxidants include, but are not limited to, sulfurized olefins characterized by the type of olefin used in the production and the final sulfur content of the antioxidant. High molecular weight olefins, that is, olefins having an average molecular weight of 168 to 351 g / mol are preferred. Examples of olefins that can be used include alpha olefins, isomerized alpha olefins, branched olefins, cyclic olefins, and combinations thereof.

Alpha olefins include, but are not limited to, any C _{4 to} C ₂₅ alpha olefin. Alpha olefins may be isomerized prior to or during the sulfurization reaction. Alpha olefin structures and / or conformers containing internal double bonds and / or branches may also be used. For example, isobutylene is a branched olefin counterpart of 1-butene, which is an alpha olefin.

  As sulfur sources that can be used in the olefin sulfurization reaction: elemental sulfur, sulfur monochloride, sulfur dichloride, sodium sulfide, sodium polysulfide, and these added together with or at various stages of the sulfurization process A mixture is mentioned.

  Unsaturated oils may also be sulfurized and used as antioxidants because they are unsaturated. Examples of oils that can be used include corn oil, canola oil, cottonseed oil, grape seed oil, olive oil, palm oil, peanut oil, coconut oil, rapeseed oil, safflower seed oil, sesame oil, soybean oil, sunflower seed oil, tallow, and These combinations are mentioned.

The amount of sulfurized olefin or fatty oil delivered to the final lubricant is based on the sulfur content of the sulfurized olefin or fatty oil and the desired level of sulfur to be delivered to the final lubricant. For example, a sulfurized fatty oil or olefin containing 20 wt% sulfur delivers 2000 ppm sulfur to the final lubricant when added to the final lubricant at a processing level of 1.0 wt%. A sulfurized fatty oil or olefin containing 10% by weight sulfur delivers 1000 ppm sulfur to the final lubricant when added to the final lubricant at a processing level of 1.0% by weight. The sulfurized olefin or sulfurized fatty oil desirably delivers between 200 ppm and 2000 ppm sulfur to the final lubricant. The total amount of antioxidant in the lubricating fluid composition described herein may range from about 0.01 to about 3.0% by weight, based on the total weight of the fluid composition. As a further example, the antioxidant may be present in an amount from about 0.1% to about 1.0% by weight.
Seal swelling agent

The lubricating compositions described herein may optionally contain a seal lubricant such as an alcohol, alkyl benzene, substituted sulfolane or mineral oil that causes the elastomeric material to swell. The alcohol-based seal swelling agent is a low-volatile linear aralkyl alcohol. Examples of suitable alcohols include decyl alcohol, tridecyl alcohol and tetradecyl alcohol. Examples of alkylbenzenes useful as seal swell agents for use in combination with the compositions described herein include dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene, and the like. Examples of substituted sulfolanes are described in US Pat. No. 4,029,588, incorporated herein by reference. Mineral oils useful as seal swell agents are typically low viscosity mineral oils with high naphthene or aromatic content. Seal swelling agents, when used in the lubricating compositions described herein, are typically about 1 to about 30% by weight, preferably about 2 to about 20% by weight, based on the total weight of the lubricating composition. %, Most preferably about 5 to about 15% by weight.
Antifoam

In some embodiments, the antifoaming agent may form another component suitable for use in the lubricating compositions described herein. The antifoaming agent may be selected from silicone, polyacrylate and the like. The amount of antifoam in the engine lubricant formulation described herein may range from about 0.001% to about 0.1% by weight, based on the total weight of the formulation. As a further example, the antifoaming agent may be present in an amount from about 0.004% to about 0.10% by weight.

  The additives used to form the compositions described herein may be individually blended into the base oil or blended in various subcombinations. However, it is preferred to blend all ingredients using the additive concentrate (ie, additive + diluent, eg hydrocarbon solvent) simultaneously. The use of additive concentrates takes advantage of the mutual compatibility imparted by the combination of ingredients when in the form of an additive concentrate. The use of concentrate also reduces blending time and reduces the possibility of blending errors.

実施例 In general, suitable lubricating fluids may include additive components within the ranges listed in the table below.

Example

The following non-limiting examples are provided to further illustrate the features and advantages of one or more embodiments of the present disclosure. All fluids tested in the following table included the ingredients shown in Table 2 to provide a fully formulated lubricating fluid composition. In the table, ultra high pressure / antiwear agent (DMTD) is a 2,5-bis- (having a ratio of about 85% bishydrocarbyl to 15% monohydrocarbyl, referred to in the table as “thiadiazole”. Hydrocarbyldithio) -1,3,4-thiadiazole and its mono-substituted equivalent, 2-hydrocarbylthio-5-mercapto-1,3,4-thiadiazole. A specific modifier of the disclosed embodiment, the friction modifier (FM1), is made with a mixture of olefins wherein at least 40% by weight of the olefin is a C ₁₀ -C ₃₆ vinylidene olefin as described above, and the friction modifier ( FM2) was made with conventional linear α-olefins. All weights of the components in the table are based on the weight of the components in the final lubricant composition.

As shown in the working examples, in specific examples 2 and 3, the use of a specific combination of DMTD and FM1 is a low temperature Brookfield viscosity (BV) less than 14,000 cp at −40 ° C., aluminum beaker oxidation test ( It is effective to impart a lead loss of less than 0.5% by weight of ABOT) and a low speed friction device (LVFA) durability of more than 300 hours. In Examples 1 to 3, the DMTD sulfur is 588 to 700 ppm by weight, the FM1 nitrogen is 192 to 480 ppm by weight, and the N / S (FM1 / DMTD) is 0.327 to 0.686. Gave the ratio.

  In Comparative Examples 1 and 2 (Comparative Example 1 and Comparative Example 2), the lubricant composition did not contain FM1, resulting in an N / S ratio of 0. Therefore, the BV and ABOT weight loss at −40 ° C. was within range, but the fluid durability was less than the minimum value of 300 hours. In Comparative Examples 5 and 6 (Comparative Examples 5 and 6), the amount of FM2 was increased in an attempt to compensate for the loss of FM1 in the lubricant composition. However, in both Comparative Example 5 and Comparative Example 6, ABOT and LVFA did not operate because the low-temperature viscosity (BV-40 ° C.) was too high.

  In Comparative Example 4 (Comparative Example 4) and Comparative Example 7 (Comparative Example 7), the amount of nitrogen by FM1 was greater than about 800, resulting in a too low temperature viscosity (BV-40 ° C.). In Comparative Example 3 (Comparative Example 3) and Comparative Example 4, the N / S ratio was too high, resulting in too large ABOT weight loss.

  Other embodiments of the disclosure will be apparent to those skilled in the art from the specification and practice of the invention disclosed herein. “A” and / or “an” as used throughout this specification and claims may refer to one or more than one. Unless otherwise indicated, all numbers expressing amounts of ingredients, properties, such as molecular weight,%, weight%, ratio, reaction conditions, etc. in this specification and claims are in all cases the term “about”. Should be understood to be modified by Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending on the desired properties sought to be obtained by the present invention. At least as an attempt to limit the application of the doctrine of claims, each numerical parameter is at least interpreted by applying conventional peripheral techniques, taking into account the number of significant figures reported. Should be. Although the numerical ranges and parameters describing the broad scope of the invention are approximations, the numerical values set forth in the examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. The true scope and spirit of the invention is set forth in the following claims, and the specification and examples are intended to be considered exemplary only.

式中、Ｒ_ｃおよびＲ_ｄは、独立して、（Ｃ_３〜Ｃ_１５）アルキル、シクロアルキルまたはシクロアルケニルである、によって表される、潤滑剤組成物。 The main features and aspects of the present invention are as follows.
1. A lubricant composition comprising:
a) a base oil;
b) 2,5-dimercapto-1,3,4-thiadiazole (DMTD), a derivative of DMTD, or a mixture thereof;
c) a friction modifier,
and that i) at least 40% by weight to impart C ₁₀ -C ₃₆ olefin maleic vinylidene olefins, the first reaction product is reacted with an anhydride, or ester,
ii) amination of the reaction product with an effective amount of a basic nitrogen-containing compound to provide a friction modifier;
A friction modifier produced by
And a C ₁₀ -C ₃₆ vinylidene olefin is represented by the following formula:

A lubricant composition represented by: wherein R _c and R _d are independently (C ₃ -C ₁₅ ) alkyl, cycloalkyl, or cycloalkenyl.

2. The lubricant of claim 1, wherein the DMTD or DMTD derivative, or mixture thereof provides about 100 to about 2000 ppm by weight sulfur to the lubricant composition, based on the total weight of the lubricant composition. Composition.

3. The lubricant of claim 1, wherein the DMTD or DMTD derivative, or mixture thereof provides about 500 to about 800 ppm by weight sulfur to the lubricant composition, based on the total weight of the lubricant composition. Composition.

4. The lubricant composition of claim 1, wherein the friction modifier (c) imparts about 50 to about 800 ppm by weight of nitrogen to the lubricant composition, based on the total weight of the lubricant composition.

5. The lubricant composition of claim 1, wherein the friction modifier (c) imparts about 150 to about 500 ppm by weight of nitrogen to the lubricant composition, based on the total weight of the lubricant composition.

6. The weight ratio of nitrogen (ppm) by friction modifier (c) to sulfur (ppm) by the DMTD or DMTD derivative or mixture thereof (b) is about 0.25: 1 to about 1.25: 1. 2. The lubricant composition according to 1 above, wherein

7. The weight ratio of nitrogen (ppm) by friction modifier (c) to sulfur (ppm) by the DMTD or DMTD derivative or mixture thereof (b) is from about 0.3: 1 to about 0.75: 1. 2. The lubricant composition according to 1 above, wherein

8.c ₁₀ -C ₃₆ vinylidene olefins, maleic thermal ene reaction conditions, reacts with the anhydride, or ester lubricant composition according to claim 1.

9. The lubricant composition of claim 1, wherein the base oil comprises greater than about 30% by weight of the total weight of the lubricant composition.

10. A transmission fluid comprising the lubricant composition according to 1 above.

11. The transmission fluid of claim 10, wherein the fluid has a low temperature Brookfield viscosity of less than 14,000 centipoise (cp) at -40 ° C.

12. The transmission fluid of claim 11, wherein the fluid has a lead coupon weight loss of less than 0.5 wt% in a 100 hour aluminum beaker oxidation test (ABOT).

13. The transmission fluid of claim 12, wherein the fluid has a low-speed friction device (LVFA) durability at 40 ° C. for more than 300 hours.

式中、Ｒ_ｃおよびＲ_ｄは、独立して、（Ｃ_３〜Ｃ_１５）アルキル、シクロアルキルまたはシクロアルケニルである、によって表される、変速機。 14. A vehicle transmission including a lubricant composition,
The lubricant composition is
a) a base oil;
b) 2,5-dimercapto-1,3,4-thiadiazole (DMTD), a derivative of DMTD, or a mixture thereof;
c) a friction modifier,
and that i) at least 40% by weight to impart C ₁₀ -C ₃₆ olefin maleic vinylidene olefins, the first reaction product is reacted with an anhydride, or ester,
ii) amination of the reaction product with an effective amount of a basic nitrogen-containing compound to provide a friction modifier;
A friction modifier produced by
And a C ₁₀ -C ₃₆ vinylidene olefin is represented by the following formula:

A transmission in which R _c and R _d are independently represented by (C ₃ -C ₁₅ ) alkyl, cycloalkyl, or cycloalkenyl.

15. The transmission of claim 14, wherein the DMTD or DMTD derivative, or mixture thereof provides about 100 to about 2000 ppm by weight sulfur to the lubricating fluid based on the total weight of the lubricant composition.

16. The transmission of claim 14, wherein the friction modifier (c) imparts about 50 to about 800 ppm by weight of nitrogen to the lubricant composition, based on the total weight of the lubricant composition.

17. The weight ratio of nitrogen (ppm) by friction modifier (c) to sulfur (ppm) by the DMTD or DMTD derivative or mixture thereof (b) is about 0.25: 1 to about 1.25: 1. 15. The transmission according to the above 14, which is a range of

式中、Ｒ_ｃおよびＲ_ｄは、独立して、（Ｃ_３〜Ｃ_１５）アルキル、シクロアルキルまたはシクロアルケニルである、によって表される、方法。 18. A method for providing a multi-vehicle transmission fluid comprising the steps of:
Oil of lubricating viscosity
i) about 100 to about 2000 ppm by weight of 2,5-dimercapto-1,3,4-thiadiazole (DMTD), a derivative of DMTD, or a mixture thereof in terms of the sulfur content of the transmission fluid derived from component (i) When,
ii) about 50 to about 800 ppm of friction modifier in terms of nitrogen content, based on the total weight of the friction modifier transmission fluid;
Blending with,
The friction modifier is
a) at least 40% by weight of C ₁₀ -C ₃₆ vinylidene olefin maleic acid containing olefin, and applying the first reaction product is reacted with an anhydride, or ester,
b) aminating the first reaction product with an effective amount of a basic nitrogen-containing compound to provide a friction modifier;
Produced by
The _C 10 _{-C 36} vinylidene olefins, the following formula:

A method wherein R _c and R _d are independently (C ₃ -C ₁₅ ) alkyl, cycloalkyl or cycloalkenyl.

19. The weight ratio of nitrogen (ppm) with friction modifier (ii) to sulfur (ppm) with said DMTD or DMTD derivative or mixture thereof (i) is about 0.25: 1 to about 1.25: 1. 19. The method according to 18 above, which is in the range of

20. The method of claim 18, wherein the transmission fluid has a low temperature Brookfield viscosity of less than 14,000 centipoise (cp) at -40 ° C.

21. The method of claim 18, wherein the transmission fluid has a lead coupon weight loss of less than 0.5 wt% in a 100 hour aluminum beaker oxidation test (ABOT).

22. The method of claim 18, wherein the transmission fluid has a low speed friction device (LVFA) durability of greater than 300 hours at 40 ° C.

Claims (17)

A lubricant composition comprising:
a) a base oil;
b) 2,5-dimercapto-1,3,4-thiadiazole (DMTD), a derivative of DMTD, or a mixture thereof;
c) a friction modifier,
i) acid catalysis is reacted under the conditions treated at least 40% by weight C ₁₀ -C ₃₆ olefin maleic vinylidene olefin, imparting a first reaction product is reacted with the anhydride or ester thereof, To do
ii) amination of the reaction product with an effective amount of a basic nitrogen-containing compound to provide a friction modifier;
A friction modifier produced by
A C ₁₀ -C ₃₆ vinylidene olefin is represented by the following formula:

Wherein R _c and R _d are independently represented by (C ₃ -C ₁₅ ) alkyl, cycloalkyl or cycloalkenyl,
Wherein the friction modifier c) imparts 50-800 ppm by weight of nitrogen to the lubricant composition, based on the total weight of the lubricant composition, and the nitrogen (ppm) by the friction modifier c) versus the above The weight ratio of sulfur (ppm) by DMTD or DMTD derivative or mixture thereof b) is in the range of 0.25: 1 to 1.25: 1 .
A lubricant composition characterized by that. The lubricant composition of claim 1, wherein the DMTD or DMTD derivative, or mixture thereof provides 100 to 2000 ppm by weight of sulfur to the lubricant composition, based on the total weight of the lubricant composition. The lubricant composition of claim 1, wherein the DMTD or DMTD derivative, or mixture thereof provides 500 to 800 ppm by weight of sulfur to the lubricant composition based on the total weight of the lubricant composition. The lubricant composition of claim 1, wherein the friction modifier (c) imparts 150 to 500 ppm by weight of nitrogen to the lubricant composition, based on the total weight of the lubricant composition. The weight ratio of nitrogen (ppm) by the friction modifier (c) to sulfur (ppm) by the DMTD or DMTD derivative or a mixture thereof (b) is in the range of 0.3: 1 to 0.75: 1. The lubricant composition according to claim 1. The lubricant composition of claim 1, wherein the C ₁₀ -C ₃₆ vinylidene olefin reacts with maleic acid, its anhydride, or its ester under thermal ene reaction conditions. The lubricant composition of claim 1, wherein the base oil comprises more than 30 % by weight of the total weight of the lubricant composition.   A transmission fluid comprising the lubricant composition of claim 1. The transmission fluid of claim 8, wherein the fluid has a low temperature Brookfield viscosity of less than 14,000 centipoise (cp) at −40 ° C. The transmission fluid of claim 9, wherein the fluid has a lead coupon weight loss of less than 0.5 wt% in a 100 hour aluminum beaker oxidation test (ABOT).   The transmission fluid of claim 10, wherein the fluid has a low speed friction device (LVFA) durability of greater than 300 hours at 40 ° C. A vehicle transmission comprising a lubricant composition,
The lubricant composition is
a) a base oil;
b) 2,5-dimercapto-1,3,4-thiadiazole (DMTD), a derivative of DMTD, or a mixture thereof;
c) a friction modifier,
i) acid catalysis is reacted under the conditions treated at least 40% by weight C ₁₀ -C ₃₆ olefin maleic vinylidene olefin, imparting a first reaction product is reacted with the anhydride or ester thereof, To do
ii) amination of the reaction product with an effective amount of a basic nitrogen-containing compound to provide a friction modifier;
A friction modifier produced by
A C ₁₀ -C ₃₆ vinylidene olefin is represented by the following formula:

Wherein R _c and R _d are independently represented by (C ₃ -C ₁₅ ) alkyl, cycloalkyl or cycloalkenyl,
Wherein the friction modifier c) imparts 50-800 ppm by weight of nitrogen to the lubricant composition, based on the total weight of the lubricant composition, and the nitrogen (ppm) by the friction modifier c) versus the above The weight ratio of sulfur (ppm) by DMTD or DMTD derivative or mixture thereof b) is in the range of 0.25: 1 to 1.25: 1 .
A transmission characterized by that. The transmission of claim 12, wherein the DMTD or DMTD derivative, or mixture thereof imparts 100 to 2000 ppm by weight of sulfur to the lubricating fluid based on the total weight of the lubricant composition. A method for providing a multi-vehicle transmission fluid comprising:
Oil of lubricating viscosity,
i) 100 to 2000 ppm by weight of 2,5-dimethylcapto-1,3,4-thiadiazole (DMTD), a derivative of DMTD, or a mixture thereof, in terms of the sulfur content of the transmission fluid derived from component (i) ,
ii) 50 to 800 ppm of friction modifier in terms of nitrogen content based on the total weight of the transmission fluid;
Blending,
The friction modifier is
a) an acid catalyzed reacted under the conditions treated at least 40% by weight of C ₁₀ -C ₃₆ vinylidene olefin maleic acid containing olefin, anhydride, or first reaction product is reacted with an ester thereof Granting,
b) aminating the first reaction product with an effective amount of a basic nitrogen-containing compound to provide a friction modifier;
Produced by
The C ₁₀ -C ₃₆ vinylidene olefins, the following formula:

Wherein R _c and R _d are independently represented by (C ₃ -C ₁₅ ) alkyl, cycloalkyl or cycloalkenyl,
Here, the weight ratio of nitrogen (ppm) by the friction modifier c) to sulfur (ppm) by the DMTD or DMTD derivative or their mixed part b) is in the range of 0.25: 1 to 1.25: 1 . is there,
A method characterized by that. The method of claim 14, wherein the transmission fluid has a cold Brookfield viscosity of less than 14,000 centipoise (cp) at −40 ° C. The transmission fluid was reduced to 0.1 in a 100 hour aluminum beaker oxidation test (ABOT).
15. The method of claim 14, having a lead coupon weight loss of less than 5% by weight.   The method of claim 14, wherein the transmission fluid has a low speed friction device (LVFA) durability of greater than 300 hours at 40 ° C.